WO2014049958A1 - Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux utilisant ledit matériau actif d'électrode positive - Google Patents

Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux utilisant ledit matériau actif d'électrode positive Download PDF

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WO2014049958A1
WO2014049958A1 PCT/JP2013/005076 JP2013005076W WO2014049958A1 WO 2014049958 A1 WO2014049958 A1 WO 2014049958A1 JP 2013005076 W JP2013005076 W JP 2013005076W WO 2014049958 A1 WO2014049958 A1 WO 2014049958A1
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positive electrode
active material
lithium
electrode active
transition metal
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PCT/JP2013/005076
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Japanese (ja)
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純一 菅谷
学 滝尻
正信 竹内
柳田　勝功
毅 小笠原
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三洋電機株式会社
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Priority to US14/420,718 priority Critical patent/US20150221942A1/en
Priority to JP2014538118A priority patent/JP6124309B2/ja
Priority to CN201380046602.4A priority patent/CN104603997A/zh
Publication of WO2014049958A1 publication Critical patent/WO2014049958A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/0042—Four or more solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the positive electrode active material.
  • a non-aqueous electrolyte secondary battery that performs charge / discharge by moving lithium ions between the positive and negative electrodes along with charge / discharge has a high energy density and a high capacity. Widely used as a drive power source.
  • non-aqueous electrolyte secondary batteries have attracted attention as power sources for power tools and electric vehicles, and are expected to expand their applications.
  • a power source is required to have a high capacity so that it can be used for a long time and to improve cycle characteristics when a large current is repeatedly discharged in a relatively short time.
  • it is essential to achieve high capacity while maintaining cycle characteristics under large current discharge.
  • Patent Document 1 A proposal for suppressing an increase in float current during high-temperature charging by allowing an oxide such as Gd to be present on the surface of a base material particle capable of occluding and releasing lithium ions (see Patent Document 1). (2) A proposal for improving cycle characteristics and storage characteristics by allowing more elements such as Zr to be present in the vicinity of the secondary particle surface of the positive electrode active material (see Patent Document 2).
  • the positive electrode active material is cracked when discharged with a large current, and a new surface of the primary particles is exposed, and the positive electrode active material and the electrolysis on the new surface are exposed.
  • the side reaction with the liquid cannot be sufficiently suppressed. For this reason, when discharging with a large current is repeatedly performed, there is a problem that the battery capacity is reduced, the cycle characteristics are lowered, and the output characteristics are lowered.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery includes a lithium-containing transition metal oxide composed of secondary particles containing nickel and zirconium and aggregated primary particles, and an interface where the primary particles are in contact with each other. And / or a rare earth compound adhering to the vicinity of the interface.
  • FIG. 1 is a schematic longitudinal sectional view showing a schematic structure of a cylindrical nonaqueous electrolyte secondary battery according to one embodiment of the present invention.
  • a lithium-containing transition metal oxide composed of secondary particles containing nickel and zirconium and aggregated primary particles and the interface between the primary particles and / or adhering to the vicinity of the interface.
  • a rare earth compound When the lithium-containing transition metal oxide is present in the form of secondary particles, if a rare earth compound is attached to the interface where primary particles are in contact with each other and / or the vicinity of the interface, the interface and / or the interface In the vicinity, there will be a zirconium and rare earth compound contained in the lithium-containing transition metal oxide.
  • the battery according to one embodiment of the present invention is extremely useful in tool applications and the like that need to be discharged with a large current of 10 A and 20 A.
  • zirconium exists uniformly in the primary particles of the lithium-containing transition metal oxide, or exists in a large amount on the surface and / or surface layer of the primary particles (near the surface inside the primary particles). In addition, a large amount may exist on the surface and / or surface layer of the secondary particles.
  • the lithium-containing transition metal oxide has the composition formula Li x Ni y Zr z M (1-yz) O 2 (0.9 ⁇ x ⁇ 1.2, 0.3 ⁇ y ⁇ 0.9, 0.001 ⁇ z ⁇ 0.01) is preferable.
  • the value of x is preferably 0.9 ⁇ x ⁇ 1.2, but a more preferable value is 0.98 ⁇ x ⁇ 1.05. If the value of x is 0.95 or less, the stability of the crystal structure is lowered, so that it is not sufficient to maintain the capacity during the passage of the cycle and to suppress the deterioration of the output characteristics. On the other hand, when the value of x is 1.2 or more, gas generation increases.
  • the reason why the value of y is regulated as described above is that when the value of y is 0.3 or less, the discharge capacity decreases. Further, if the value of y exceeds 0.9, the stability of the crystal structure is lowered, so that it is not sufficient to maintain the capacity during the cycle and to suppress the deterioration of the output characteristics.
  • the value of z is preferably 0.001 ⁇ z ⁇ 0.01, but a more preferable value is 0.003 ⁇ z ⁇ 0.007. If the value of z is less than 0.001, the presence effect of zirconium is reduced. Moreover, it is because discharge capacity will fall when the value of z exceeds 0.01.
  • the lithium-containing transition metal oxide the composition formula Li x Ni y Zr z Co a Mn b Al (1-yzab) O 2 (0.9 ⁇ x ⁇ 1.2,0.3 ⁇ y ⁇ 0. 9, 0.001 ⁇ z ⁇ 0.01, yb> 0.03, and 0 ⁇ b ⁇ 0.5).
  • yb> 0.03 is that when the composition ratio of Mn is high, an impurity phase is generated, resulting in a decrease in capacity and a decrease in output. Therefore, yb is preferably 0 or more. by.
  • the primary particle diameter of the lithium-containing transition metal oxide is preferably 0.2 ⁇ m or more and 2 ⁇ m or less, and particularly preferably 0.5 ⁇ m or more and 1 ⁇ m or less. If the primary particle diameter is less than 0.2 ⁇ m, the number of interfaces where the primary particles contact each other increases, so that a rare earth compound adheres to the interface where the primary particles contact each other and / or near the interface. The proportion that is reduced. Therefore, a stable structure may not be sufficiently formed on the primary particle surface of the lithium-containing transition metal oxide, and the effect of improving the cycle characteristics and the effect of suppressing the decrease in output characteristics may be insufficient. On the other hand, when the primary particle diameter exceeds 2 ⁇ m, the diffusion characteristic of lithium ions in the lithium-containing transition metal oxide becomes long during large current discharge, and thus the output characteristics deteriorate.
  • the rare earth compound is preferably a rare earth hydroxide, a rare earth oxyhydroxide, or a rare earth oxide, and in particular, a rare earth hydroxide or a rare earth oxyhydroxide. desirable. This is because when these are used, the above-described effects are further exhibited.
  • the rare earth compound may partially contain a rare earth carbonate compound, a rare earth phosphate compound, or the like.
  • rare earth elements contained in the rare earth compounds include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • Samarium and erbium are preferable. This is because a neodymium compound, a samarium compound, and an erbium compound have a smaller average particle diameter than other rare earth compounds, and are more likely to be deposited more uniformly on the surface of the positive electrode active material.
  • the rare earth compound examples include neodymium hydroxide, neodymium oxyhydroxide, samarium hydroxide, samarium oxyhydroxide, erbium hydroxide, erbium oxyhydroxide and the like. Further, when lanthanum hydroxide or lanthanum oxyhydroxide is used as the rare earth compound, lanthanum is inexpensive, so that the manufacturing cost of the positive electrode can be reduced.
  • the average particle size of the rare earth compound is desirably 1 nm or more and 100 nm or less. If the average particle size of the rare earth compound exceeds 100 nm, the particle size of the rare earth compound becomes too large, so that the number of particles of the rare earth compound decreases. For this reason, the probability that the rare earth compound adheres to the interface where the primary particles are in contact with each other and / or the vicinity of the interface decreases.
  • the average particle size of the rare earth compound is less than 1 nm, the lithium-containing transition metal oxide particle surface is too densely covered with the rare-earth compound, so that lithium ions are occluded on the lithium-containing transition metal oxide particle surface. , The discharge performance is degraded, and the charge / discharge characteristics are degraded.
  • the average particle size of the rare earth compound is more preferably 10 nm or more and 50 nm or less.
  • a rare earth compound such as erbium oxyhydroxide
  • an aqueous solution in which an erbium salt is dissolved is mixed with a solution in which the lithium-containing transition metal oxide is dispersed, and the lithium-containing transition metal is mixed.
  • An example is a method in which a rare earth element salt is deposited on the surface of the oxide and then heat-treated.
  • the heat treatment temperature is preferably 120 ° C. or higher and 700 ° C. or lower, and more preferably 250 ° C. or higher and 500 ° C. or lower. When the temperature is lower than 120 ° C., the moisture adsorbed on the active material is not sufficiently removed, so that there is a possibility that moisture is mixed in the battery.
  • the temperature exceeds 700 ° C.
  • the rare earth compound adhering to the surface diffuses into the inside, making it difficult to be present on the surface of the active material, making it difficult to obtain an effect.
  • the temperature is set to 250 ° C. to 500 ° C.
  • moisture can be removed and a state where a rare earth compound is selectively attached to the surface can be formed. If it exceeds 500 ° C., a part of the rare earth compound on the surface diffuses inside, and the effect may be reduced.
  • aqueous solution in which a salt of a rare earth element (for example, erbium salt) is dissolved is sprayed and then mixed with a lithium-containing transition metal oxide and then dried.
  • a lithium-containing transition metal oxide and a rare earth compound are mixed using a mixing processor, and the rare earth compound is mechanically attached to the surface of the lithium-containing transition metal oxide.
  • the heat treatment temperature in this case is the same as the heat treatment temperature in the method of mixing the above aqueous solution.
  • a solution in which a rare earth salt such as an erbium salt is dissolved is mixed with a solution in which a lithium-containing transition metal oxide is dispersed, or a salt of a rare earth element is mixed while mixing a lithium-containing transition metal oxide. It is preferable to use a method in which a dissolved aqueous solution is sprayed, and it is particularly preferable to use a method in which an aqueous solution in which a rare earth salt such as an erbium salt is dissolved is mixed with a solution in which a lithium-containing transition metal oxide is dispersed. This is because, in this method, the rare earth compound can be more uniformly dispersed and adhered to the surface of the lithium-containing transition metal oxide.
  • the pH of the solution in which the lithium-containing transition metal oxide is dispersed constant, and in particular, in order to uniformly disperse fine particles of 1 to 100 nm on the surface of the lithium-containing transition metal oxide, It is preferable to regulate the pH to 6-10.
  • the pH is less than 6, the transition metal of the lithium-containing transition metal oxide may be eluted.
  • the pH exceeds 10, the rare earth compound may be segregated.
  • the ratio of the rare earth element to the total molar amount of the transition metal in the lithium-containing transition metal oxide is preferably 0.003 mol% or more and 0.25 mol% or less.
  • the proportion is less than 0.003 mol%, the effect of attaching the rare earth compound may not be sufficiently exerted, whereas when the proportion exceeds 0.25 mol%, the lithium-containing transition metal oxide particles The reactivity at the surface is lowered, and the cycle characteristics in a large current discharge may be deteriorated.
  • the solvent of the nonaqueous electrolyte is not particularly limited, and a solvent that has been conventionally used for nonaqueous electrolyte secondary batteries can be used.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, propionic acid
  • esters such as ethyl and ⁇ -butyrolactone
  • compounds containing sulfone groups such as propane sultone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, 1,4 -Compounds containing ethers such as dioxane and 2-methyltetrahydrofuran, butyronitrile,
  • a solvent in which a part of these H is substituted with F is preferably used. Further, these can be used alone or in combination, and a solvent in which a cyclic carbonate and a chain carbonate are combined, and a solvent in which a compound containing a small amount of nitrile or an ether is further combined with these is preferable. .
  • An ionic liquid can also be used as the non-aqueous solvent of the non-aqueous electrolyte.
  • the cation species and the anion species are not particularly limited, but low viscosity, electrochemical stability, hydrophobic properties are not limited. From the viewpoint, a combination using a pyridinium cation, an imidazolium cation, or a quaternary ammonium cation as the cation and a fluorine-containing imide anion as the anion is particularly preferable.
  • a known lithium salt that has been conventionally used in nonaqueous electrolyte secondary batteries can be used.
  • a lithium salt a lithium salt containing one or more elements among P, B, F, O, S, N, and Cl can be used.
  • LiPF 6 LiBF 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), Lithium salts such as LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6 , LiClO 4 , LiPF 2 O 2 and mixtures thereof can be used.
  • LiPF 6 is preferably used in order to enhance the high rate charge / discharge characteristics and durability of the nonaqueous electrolyte secondary battery.
  • a lithium salt having an oxalato complex as an anion can also be used.
  • the lithium salt having the oxalato complex as an anion include LiBOB [lithium-bisoxalate borate] and a lithium salt having an anion in which C 2 O 4 2 ⁇ is coordinated to the central atom, for example, Li [M (C 2 O 4 ) x R y ] (wherein M is a transition metal, an element selected from Groups 13, 14, and 15 of the periodic table, R is selected from a halogen, an alkyl group, and a halogen-substituted alkyl group) Group, x is a positive integer, and y is 0 or a positive integer).
  • the said solute may be used not only independently but in mixture of 2 or more types.
  • the concentration of the solute is not particularly limited, but is preferably 0.8 to 1.7 mol per liter of the electrolyte.
  • the concentration of the solute is desirably 1.0 to 1.6 mol per liter of the electrolyte.
  • the negative electrode active material is not particularly limited as long as it can reversibly occlude and release lithium.
  • a carbon material, a metal or alloy material alloyed with lithium, a metal oxide, or the like is used. be able to.
  • a carbon material for the negative electrode active material For example, natural graphite, artificial graphite, mesophase pitch-based carbon fiber (MCF), mesocarbon microbeads (MCMB), coke, hard carbon Etc. can be used.
  • MCF mesophase pitch-based carbon fiber
  • MCMB mesocarbon microbeads
  • coke hard carbon Etc.
  • a carbon material obtained by coating a graphite material with low crystalline carbon is preferable to use.
  • the separator conventionally used can be used. Specifically, not only a separator made of polyethylene but also a material in which a layer made of polypropylene is formed on the surface of polyethylene or a material in which an aramid resin is applied on the surface of a polyethylene separator may be used.
  • a layer containing an inorganic filler that has been conventionally used can be formed at the interface between the positive electrode and the separator or the interface between the negative electrode and the separator.
  • the filler it is also possible to use an oxide or a phosphoric acid compound that uses titanium, aluminum, silicon, magnesium, etc., which has been used conventionally or a plurality thereof, and whose surface is treated with a hydroxide or the like. it can.
  • the filler layer is formed by a method in which a filler-containing slurry is directly applied to a positive electrode, a negative electrode, or a separator, or a method in which a sheet formed with a filler is attached to a positive electrode, a negative electrode, or a separator. be able to.
  • the obtained transition metal oxide was a single phase belonging to the space group R3-m.
  • the composition was LiNi 0.545 Co 0.20 Mn 0.25 Zr 0.005 O 2 . From the results of SEM observation, it was confirmed that the lithium-containing transition metal oxide was composed of secondary particles in which primary particles (average particle diameter by SEM observation was 0.7 ⁇ m) were aggregated.
  • the average particle diameter (D50) of the secondary particles was 14 ⁇ m.
  • the average particle size (D50) of the secondary particles is obtained by integrating the mass of the particles in order from the smallest particle size using a laser diffraction particle size distribution measuring device, and the accumulated mass is 50 of the mass of all particles. It calculated
  • the adhesion amount of the said erbium oxyhydroxide was 0.1 mol% with respect to the total molar amount of the transition metal of the said lithium containing transition metal oxide in conversion of an erbium element. Further, when the obtained positive electrode active material was observed with an SEM, it was confirmed that erbium oxyhydroxide was attached to the interface where primary particles in the lithium-containing transition metal oxide were in contact with each other and / or in the vicinity of the interface. did.
  • negative electrode 97.5 parts by mass of artificial graphite as a negative electrode active material, 1 part by mass of carboxymethyl cellulose as a thickener, and 1.5 parts by mass of styrene butadiene rubber as a binder are mixed, and an appropriate amount of pure water is mixed. In addition, a negative electrode slurry was prepared. Next, this negative electrode slurry was applied to both sides of a negative electrode current collector made of copper foil and dried. Finally, it was cut into a predetermined electrode size, rolled using a roller, and a negative electrode lead was attached to produce a negative electrode.
  • the positive electrode and the negative electrode were arranged to face each other via a separator made of a polyethylene microporous film, and then wound in a spiral shape using a winding core. Next, the winding core is pulled out to produce a spiral electrode body, and after inserting the electrode body into a metal outer can, the non-aqueous electrolyte is injected and further sealed, so that the battery size becomes the diameter.
  • a 18650 type nonaqueous electrolyte secondary battery (theoretical amount: 2.0 Ah) of 18 mm and a height of 65 mm was produced. The battery thus produced is hereinafter referred to as battery A.
  • FIG. 1 is a schematic cross-sectional view of the nonaqueous electrolyte secondary battery produced as described above.
  • Reference numeral 1 denotes a nonaqueous electrolyte secondary battery
  • 10 denotes an electrode body
  • 11 denotes a positive electrode
  • 12 denotes a negative electrode.
  • 16 is a separator
  • 17 is a battery container.
  • battery A has an increased number of cycles to reach the 70% capacity maintenance ratio and a smaller increase in resistance with the passage of cycles than batteries Z1 to Z3. Can be confirmed. Comparing the battery Z1 and the battery Z3 to which erbium oxyhydroxide is not attached, the battery Z1 containing zirconium has a slightly smaller increase in resistance after 150 cycles than the battery Z3 containing no zirconium. However, it is still insufficient. Moreover, it can be confirmed that the number of cycles until the capacity retention rate reaches 70% is extremely small in both batteries regardless of the presence or absence of zirconium.
  • the battery Z2 to which erbium oxyhydroxide is attached has a capacity maintenance ratio of 70 compared to the battery Z3 to which erbium oxyhydroxide is not attached.
  • zirconium is contained in the lithium-containing transition metal oxide, and the primary particles in the secondary particles of the lithium-containing transition metal oxide are in contact with each other, and / or in the vicinity of the interface, If erbium (rare earth element) of erbium oxyhydroxide is adhered, zirconium element and erbium element coexist in the vicinity of the primary particle interface. For this reason, it is thought that it is because the particle
  • the reaction mechanism for forming a stable structure at the interface and / or the vicinity thereof is not clear, but the following It seems like.
  • zirconium is contained in the lithium-containing transition metal oxide, since the valence of zirconium exists in a trivalent to tetravalent state, the 4d orbit is an empty orbit. Therefore, an interaction occurs between the 4f orbital electron, which is a characteristic of rare earth elements, and the empty 4d orbital, and the 4f orbital electron is attracted to the empty 4d orbital.
  • the electronic state of the transition metal existing around zirconium (including nickel, but also including cobalt, manganese, etc. in addition to nickel) Therefore, it is considered that a decrease in the valence of the transition metal is suppressed and a stable structure can be maintained on the surface of the lithium-containing transition metal oxide.
  • the present invention can be expected to be deployed in, for example, driving power sources for mobile information terminals such as mobile phones, notebook computers, smartphones, etc., driving power sources for high output such as electric vehicles, HEVs and electric tools, and power sources related to power storage.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un matériau actif d'électrode positive pour une batterie secondaire à électrolyte non aqueux, ledit matériau actif comprenant : un oxyde de métal de transition contenant du lithium qui contient du nickel et du zirconium et qui est composé de particules secondaires formées par l'agglomération de particules primaires ; et un composé des terres rares qui adhère à des interfaces, dans chacun desquels deux des particules primaires sont en contact l'une avec l'autre, et/ou aux environs des interfaces.
PCT/JP2013/005076 2012-09-28 2013-08-28 Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux utilisant ledit matériau actif d'électrode positive WO2014049958A1 (fr)

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US14/420,718 US20150221942A1 (en) 2012-09-28 2013-08-28 Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery including the same
JP2014538118A JP6124309B2 (ja) 2012-09-28 2013-08-28 非水電解質二次電池用正極活物質及びその正極活物質を用いた非水電解質二次電池
CN201380046602.4A CN104603997A (zh) 2012-09-28 2013-08-28 非水电解质二次电池用正极活性物质以及使用该正极活性物质的非水电解质二次电池

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WO2016031147A1 (fr) * 2014-08-26 2016-03-03 三洋電機株式会社 Matériau actif d'électrode positive de batterie secondaire à électrolyte non aqueux
WO2016103591A1 (fr) * 2014-12-26 2016-06-30 三洋電機株式会社 Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
WO2016103592A1 (fr) * 2014-12-25 2016-06-30 三洋電機株式会社 Matériau actif d'électrode positive et batterie rechargeable à électrolyte non aqueux
WO2017022222A1 (fr) * 2015-08-06 2017-02-09 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux
CN106663805A (zh) * 2014-07-30 2017-05-10 三洋电机株式会社 非水电解质二次电池用正极活性物质
JP2017117529A (ja) * 2015-12-21 2017-06-29 旭硝子株式会社 正極活物質、リチウムイオン二次電池用正極およびリチウムイオン二次電池
JPWO2018003439A1 (ja) * 2016-06-30 2019-04-18 パナソニックＩｐマネジメント株式会社 正極活物質及び非水電解質二次電池

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JP7030030B2 (ja) * 2018-08-02 2022-03-04 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質およびリチウムイオン二次電池

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WO2015125444A1 (fr) * 2014-02-19 2015-08-27 三洋電機株式会社 Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux
US10218000B2 (en) 2014-02-19 2019-02-26 Sanyo Electric Co., Ltd. Positive electrode active material for nonaqueous electrolyte secondary battery
CN106663805A (zh) * 2014-07-30 2017-05-10 三洋电机株式会社 非水电解质二次电池用正极活性物质
CN106663805B (zh) * 2014-07-30 2019-07-05 三洋电机株式会社 非水电解质二次电池用正极活性物质
CN106663804B (zh) * 2014-08-26 2019-08-06 三洋电机株式会社 非水电解质二次电池用正极活性物质
CN106663804A (zh) * 2014-08-26 2017-05-10 三洋电机株式会社 非水电解质二次电池用正极活性物质
JPWO2016031147A1 (ja) * 2014-08-26 2017-06-29 三洋電機株式会社 非水電解質二次電池用正極活物質
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WO2016031147A1 (fr) * 2014-08-26 2016-03-03 三洋電機株式会社 Matériau actif d'électrode positive de batterie secondaire à électrolyte non aqueux
WO2016103592A1 (fr) * 2014-12-25 2016-06-30 三洋電機株式会社 Matériau actif d'électrode positive et batterie rechargeable à électrolyte non aqueux
CN107112527B (zh) * 2014-12-25 2020-03-03 三洋电机株式会社 正极活性物质和非水电解质二次电池
CN107112527A (zh) * 2014-12-25 2017-08-29 三洋电机株式会社 正极活性物质和非水电解质二次电池
US10559825B2 (en) 2014-12-25 2020-02-11 Sanyo Electric Co., Ltd. Positive electrode active material and nonaqueous electrolyte secondary battery
JPWO2016103592A1 (ja) * 2014-12-25 2017-10-05 三洋電機株式会社 正極活物質及び非水電解質二次電池
JPWO2016103591A1 (ja) * 2014-12-26 2017-10-05 三洋電機株式会社 非水電解質二次電池用正極活物質及び非水電解質二次電池
US10096830B2 (en) 2014-12-26 2018-10-09 Sanyo Electric Co., Ltd. Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
WO2016103591A1 (fr) * 2014-12-26 2016-06-30 三洋電機株式会社 Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
JPWO2017022222A1 (ja) * 2015-08-06 2018-05-24 パナソニックＩｐマネジメント株式会社 非水電解質二次電池
CN107836056A (zh) * 2015-08-06 2018-03-23 松下知识产权经营株式会社 非水电解质二次电池
WO2017022222A1 (fr) * 2015-08-06 2017-02-09 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux
CN107836056B (zh) * 2015-08-06 2021-03-30 松下知识产权经营株式会社 非水电解质二次电池
US11094924B2 (en) 2015-08-06 2021-08-17 Panasonic Intellectual Property Management Co, Ltd. Nonaqueous electrolyte secondary batteries
JP2017117529A (ja) * 2015-12-21 2017-06-29 旭硝子株式会社 正極活物質、リチウムイオン二次電池用正極およびリチウムイオン二次電池
JPWO2018003439A1 (ja) * 2016-06-30 2019-04-18 パナソニックＩｐマネジメント株式会社 正極活物質及び非水電解質二次電池
US20190312274A1 (en) * 2016-06-30 2019-10-10 Panasonic Intellectual Property Management Co., Ltd. Positive electrode active material and nonaqueous electrolyte secondary battery

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